TY - JOUR

T1 - Effective radius of a contact diffusion-controlled reaction between small solutes and a polymer chain

AU - Borovkov, V. I.

AU - Chetverikov, A. O.

N1 - This work was supported by the Russian Federal Ministry of Science and Higher Education (Grant No. FWGF-2021-0003). The computer modeling of the recombination reaction was supported by the Russian Science Foundation (Project No. 21-13-00278).

PY - 2024/12/14

Y1 - 2024/12/14

N2 - The aim of this study was to develop a formula for estimating the effective radius of a diffusion-controlled irreversible contact reaction between diffusing solutes and a nonlinear immobile polymer molecule. Analytical expressions for the reaction radius were obtained that took into account averaging over conformations for chains with arbitrary segment-to-segment angles and distributions of dihedral angles. A comparison of the analytical results with the results of computer stochastic modeling of the reaction showed good agreement over a wide range of parameters. Based on an analysis of these expressions, parameter ranges were established in which it was possible to use either the linear chain or Gaussian coil approximation to describe the reaction kinetics. A comparison of several distributions over chain lengths showed that, as a first approximation, the radius of reaction can be estimated as that for a chain corresponding to the number-averaged molecular weight. Results of earlier experimental studies on charge scavenging by polymer molecules have been explained.

AB - The aim of this study was to develop a formula for estimating the effective radius of a diffusion-controlled irreversible contact reaction between diffusing solutes and a nonlinear immobile polymer molecule. Analytical expressions for the reaction radius were obtained that took into account averaging over conformations for chains with arbitrary segment-to-segment angles and distributions of dihedral angles. A comparison of the analytical results with the results of computer stochastic modeling of the reaction showed good agreement over a wide range of parameters. Based on an analysis of these expressions, parameter ranges were established in which it was possible to use either the linear chain or Gaussian coil approximation to describe the reaction kinetics. A comparison of several distributions over chain lengths showed that, as a first approximation, the radius of reaction can be estimated as that for a chain corresponding to the number-averaged molecular weight. Results of earlier experimental studies on charge scavenging by polymer molecules have been explained.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85212227633&origin=inward&txGid=b5e8e667a98ca2bf6e86ee4b0507b6b1

UR - https://www.mendeley.com/catalogue/e719f4a6-3e27-3e4a-955c-1544f0e31c95/

U2 - 10.1063/5.0242758

DO - 10.1063/5.0242758

M3 - Article

VL - 161

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 22

M1 - 224105

ER -